Manufacture of fluoroolefins



Patented Feb. 17, 1953 MANUFACTURE OF FLUOROOLEFINS Charles E. Miller, Lynbrook, N. Y., assignor to Allied Chemical & Dye Corporation, New York, N. Y., a corporation of New York No Drawing. Application November 26, 1951, Serial No. 258,291

13 Claims. (Cl. 260-653) This invention is directed to manufacture of fluoroolefinic compounds suitable for use chiefly as monomers.

A principal object of the invention lies in the provision of methods for making fluoroolefinic compounds from halofluoroalkanes by thermocatalytic procedures which may be easily controlled and carried out at moderate temperatures.

The starting materials utilized in practice of the invention comprise halofiuoroalkanes containing at least two carbon atoms and containing at least one hydrogen atom and at least one halogen (e. g. chlorine) atom other than fluorine on adjacent carbon atoms. Such starting materials include, in the better embodiments of the invention, chlorofiuoroethanes containing at least one hydrogen atom on one carbon atom and at least one chlorine atom on the other carbon atom. Representative compounds of this nature comprise CHzClCHFz, CHClzCI-IFz, CClsCHFz, and other compounds subsequently noted. The invention particularly comprehends use as starting materials of chlorofluoroethanaes containing at least one hydrogen atom and at least one chlorine atom on adjacent carbon atoms, and at least one chlorine atom and one fluorine atom on a single carbon atom, illustrative examples of this type of compound including CHzCHClF,

CHzClCHClF, CHzFCHClF, CHzFCClzF CI-IClFCI-IClF, CHCIFCClzF and CClzFCI-IFz. The preferred starting materials are chlorofiuoroethanes which contain a --CC1F2 group and at least one hydrogen atom on the adjacent carbon atom, e. g. CHaCClFz, CHzClCClFz, CHCIFCClF-z and CHClzCClFz. Although applicable to the utilization of a relatively large number of halofiuoroalkanes as starting materials, for convenience the principles of the invention may be exemplified chiefly by reference to the manufacture of vinylidene fluoride, CH2:CF2 from 1,1,1-chlorodifluoroethane, CH3CC1F2.

In accordance with the invention it has been found that the objects thereof may be effected by dehydrohalogenating the starting material to form reaction products comprising principally the sought-for fluoroolefinic compound and hydrogen halide. Thus, in the case of use of 1,1,1- chlorodifluoroethane as starting material, the reaction may be illustrated by Additionally, when the initial material is CH2C1CC1F2, CH2C1CClF2 CI-ICl:CF2+HC1 appears to take place, and when CHClzCClFz is used 2 as starting material dichloro vinylidene fluoride, CC12 CF2, and HCl are formed. In all these instances, it will be noted that the olefinic compound corresponding with the chlorofluoroethane starting material is produced.

The invention comprises principally the discovery of certain catalysis and temperature conditions which make it possible to dehydrohalogenate the starting material in such a way as to obtain good conversion and at the same time avoid use of markedly high reaction temperatures. In general, procedural steps of the invention comprise passing the starting material through a suitable reactor while maintaining therein certain catalysis-temperature-reaction conditions, discharging the reaction products from the reactor, scrubbing the product gases e. g. with water to remove hydrogen halide, drying and condensing the gases, and then fractionating the condensate to obtain the desired products.

Practice of one of the more desirable embodiments of the invention involves adherence to three principal reaction conditions which have been found to conjunctively accomplish the dehydrohalogenation objective above noted. The first of these conditions comprises the carrying out of the reaction in the presence of carbon tetrachloride, C014, it having been found that the presence of this material in the reaction zone brings about such a change in reaction conditions that the dehydrohalogenating procedure may be carried out at unexpectedly low temperatures. The function and mechanics of operation of 0014 are not clearly understood. Practice shows some relatively small loss .of C014, but on the other hand the substantial absence of C014 decomposition products in the reactor exit gas is strong evidence to the effect that C014 losses are probabiy mechanical, and that the action of the CCli closely approaches that of a true catalyst. Whatever the exact chemical functions of the C614 may be, practice shows that the overall action of C014, from a practical viewpoint, may be considered to be that of a catalyst.

The second important operational feature, which applies to all embodiments of the invention, is temperature. It-has been found that in order to obtain dehydrohalogenation and production of the sought-for fluoroolefinic compounds, in addition to maintenance of presence of C014 in the reaction zone, temperatures should be held in the range of about 500-610 C. No worthwhile reaction appears to take place at a temperature appreciably below 500 C., and on the other hand no significant operating advantages are obtained at temperatures above about 610 C. The third important factor upon which successful practice of all embodiments depends is the maintenance in the reaction zone of the substantial absence of extraneously introduced elemental chlorine as such. The presence of even a very small amount of extraneously introduced chlorine into the reaction zone upsets the reaction conditions markedly, deteriorizes formation of olefinic compounds and gives rise to chlorinolysis and resultant formation of e. g. saturated one carbon atom products which are unwanted materials in the present process.

The quantity of carbon tetrachloride utilized in practice of the invention process may vary over a relatively wide range. Any small amount of C014 which significantly catalyzes the reaction and effects formation of any appreciably greater quantity of sought-for product, than would be obtained in the absence of the C014, may be utilized. Development work indicates that for general-practice purposes CCl4, in amount in the range of 2-25% by weight based on the Weight of the incoming halofluo'roalkane, at the reaction temperatures stated brings about good conversions of startingmaterial to sought-for product. On the other hand,- quantities of CCL; up to about 200% of the weight of the starting material have been utilized and notably good conversions obtained. Hence, quantities of CCh may vary, according to particular reaction conditions and starting materials at hand, from less than say 0.5% by weight to as much as 200% by weight,

indications being that quantities of CCli in excess of the latter value do not effect any important improvements regarding conversion. It furthermore appears that within the generally preferred 2-25% C614 quantity range there does not exist a particular more restricted CCl4 quantity range N which promotes best conversions with respect to the entire class of starting materials to which practice of the invention is applicable. Best results for any particular starting material appear to depend upon optimum C014 quantity, temperature and space velocity conditions for such starting material. Space velocity per hour (volumes of reactant gas at room temperature per volume of reaction chamber per hour) while apparently not a wholly controlling factor may lie in the range of 100- 700. In general, if a moderate amount of C014 is employed, low space velocities and temperatures in the lower part of the 500*610" C. range are adequate. In the case of some starting materials, e. g. CH3CC1F2 and CH2C1CC1F'2, conversion increases sharply with a very small temperature rise when temperatures are in the upper portion of the temperature range. In these instances higher space velocity may be employed. While the above indicated overall conditions with regard to C014 quantity, temperature and absence of extraneously introduced elemental chlorine apply to all of the starting materials herein indicated, on the other hand most of such materials possess sufficiently individual characteristics to such an extent that, as to utilization of any given starting material, determination of the optimum reaction conditions of C014 quantity, temperature and space velocity are best ascertained by one or more test runs.

According to a modification of the invention, practice of the latter as above described may be carried out conjunctiv'ely'with the use of metal lic nickel. It has been found that the presence of metallic nickel in the reaction zone catalyt- 7 ically increases conversion considerably. Thus, in the practice of one desirable embodiment, the reactor may be packed with discrete metallic nickel, e. g. x 30 gauge nickel helices, or metallic nickel in any other satisfactory form. If desired, metallic nickel alone, without the presence of C014 may be used to catalyze the reaction.

The reactor employed may be of any suitable construction designed to facilitate maintenance in the reaction zone of the temperatures indicated. The reaction tube itself may be of any satisfactory material which doe not adversely affect reaction.- For example, a nickel reactor may be used, but in all instances it is also preferred to pack the reaction zone with metallic nickel should circumstances make desirable the use of the catalytic properties of metallic nickel itself or in conjunction with CC14. Other apparatus utilized, e. g. for continuously feeding and metering starting material and C014 to the reactor, and for handling exit gase of the reactor to remove HCl or otherwise purify, dry, condense and fractionate to separate and recover desired products, may be as known in the art.

In the following examples, percent conversion was measured by water scrubbing the product gases to remove and recover HCl from the product gases,- and determining by titration the HCl content of the wash water. Percent conversion wa then calculated as mols HCl liberated per mol of starting material fed to the reactor. All runs were carried out in the absence of any extraneously introduced elemental chlorine. Un-

,- less otherwise indicated, parts noted are by weight.

Example 1.In this operation, CHsCClFz in vapor form was passed at a rate of about 60 parts per hour, through an unpacked, previously used nickel reactor tube maintained at temperature of about 550 C. Conversion of starting material to CH2=CF2 of about 14% was obtained. In a comparative run, about, 50 part of CHsCClFz and about 2 parts per hour of C014 were passed through the same reactor under the same temperature conditions, and conversion of CHaCCIFz to CH2=CF2 in the range of 50-60% was obtained.

Example 2.-About 55 parts per hour of CHaCClFz were passed through an unpacked, new nickel reactor tube maintained at temperature of about 550 C. Conversion to CH2=CF2 of about 5% was obtained. About 55 parts of CHzCClFz and about 10 parts per hour of C014 were passed through the same reactor held at the same temperature, and conversion of starting material to CHz=CFz of about 40% was obtained.

Example 3.- 'In this run, about 185 parts of CHsCClFz and about 50 parts of CCl4 were passed during a periodof two hours through a previouslyused nickel reactor tube which was packed with x 23 gauge nickel helices. Temperature was maintained at about 550 C. Reactor exit gases were scrubbed with water, passed over soda lime and CaClz, and totally condensed in a trap immersed in liquid nitrogen. The scrubbing water was tiltrated with standard NaOH for HCl and HF content. The wash water had an HF/HCl ratio of 0.025. On distillation of the trap contents, there were obtained 93 parts of CH2=CF2, B. P. minus 83 C.; 40 parts of CHsCClFz, B. P. minus 9.6 C.; 40 parts CCl4,'B. P. 77 C., and only one part of intermediate material boiling within the range of minus 83 up to minus 9.6 C. Conversion to 'CHzfi'CFz amounted to about Example 4.In a run similar to that of Example 3, using the same nickel helices packed reactor of Example 3 and a temperature of about 550 C., 212 parts of CHsCClFz and 36 parts of CClr were passed through the reactor during a period of two hours. The wash water had an l-lF/I-ICl ratio of 0.029, and on distillation there were recovered 90 parts of CHz=CF2, B. P. minus 83 C.; 72 parts of CHsCClFz, B. P. minus 9.6 C.; 32 parts of CCll, B. P. 77 C., and only one part of intermediate material boiling within the range of minus 83 C. up to minus 9.6 C. Conversion to CH2=CF2 was about 69%. In both the foregoing runs no materials other than those indicated were found, thus indicating that little if any decomposition of CCh was efiected.

Example 5.--The nickel helices were removed from the reactor used in Examples 3 and 4, and a similar run was made using a total of 200 parts of CH3CClF2 and parts of C014 during a period of one hour. Conversion of starting material to CH2=CF2 of about was obtained.

Example 6.-In this run, about parts of CHsCClFz and about 10 parts of C014 per hour were passed through a previously unused nickel reactor tube packed with x 23 gauge nickel helices and maintained at temperature of about.

550 C., the HCl scrubbing water had an HF/HCI ratio of about 0.025, and conversion to CH2=CF2 of about 63% was obtained. lar to the foregoing except that no CC14 was present, I-lF/HCI ratios were of the order of 0.05, thus indicating that the presence of CCl4 appreciably reduces decomposition of the starting material.

Example 7.-In this run, the starting material was CH2ClCClF2, and a previously used nickel reactor tube was employed. 120 parts of a mixture containing about 104.4 parts of CHzClCCIF and 15.6 parts of CCh were passed thru the reactor during a period of about 90 minutes, temperature being maintained at about 600 C. About '73 parts of product were recovered in a Dry-Ice trap, and about 24 parts in a water trap. The water from the water trap had an HF/HCl ratio of about 0.03. On distillation there were recovered 52 parts of CHC1=CF2, B. P. minus 19 C.; 29 parts of CH2C1CC1F2, B. P. plus 47 C.; and 13 parts of C014, B. P. 77 C. Conversion of starting materials to CHC1=CF2 of about 70% was obtained.

Example 8.In a run similar to Example '1, carried out in the same reactor of Example 7 at temperature of about 600 C., about 92 parts of CHzClCClFz were passed through the reactor. No CCli was present in the reactor during this run. The HCl wash water had an HF/I-ICl ratio of 0.04, and conversion of starting material to CHC1=CF2 was about 42%.

Example 9.-About 55 parts per hour of CHsCClFz were passed through a new nickel reactor tube, packed with /4 X 30 gauge nickel helices, and maintained at temperature of about 550 C. No C014 was present. Conversion to CH2=CF2 thus obtained was about 21%.

Example 10.In this run, the starting material was CHzClCClFz, and the reactor employed was the same as that utilized in Examples 7 and 8 except that the reactor was packed with A X 30 gauge nickel helices. Temperature in the reactor was maintained at about 580 C., and 1187 parts of a mixture of about 1043 parts of starting material and about 144 parts of CCh was passed thru the reactor over a period of four hours. The HF/HCl content of the wash water In other runs simi- 3 6 was 0.030. Conversion to CI-ICl:CF2 was about 74%.

Example 11 .A series of three runs was carried out at temperatures in the range of 575600 C., and with the same nickel packed reactor and gas mixture of Example 10. Average conversion,

HF/HCl wash water ratio and space velocity were about 0.031 and 590 respectively.

Iclaim: l. The process for making an olefinic compound which comprises dehydrochlorinating a chlorofiuoroethane containing at least one hy-' drogen atom and at least one chlorin atom on.

adjacent carbon atoms by heating said ethane at temperature in the range of 500-6l0 C. while in the presence of C014 in amount effective to promote dehydrochlorination and while in the absence of extraneously introduced elemental ch10 rine, and recovering an olefinic compound corresponding with said ethane.

2. The process for making an olefinic com-' pound which comprises dehydrochlorinating a chlorofiuoroethane containing at least one hydrogen atom and at least one chlorine atom on adjacent carbon atoms and at least one chlorine atom and one fluorine atom on a single carbon atom by heating said ethan at temperature inpound which comprises dehydrochlorinating a chlorofiuoroethane containing a CClFz group and at least one hydrogen atom on the adjacent carbon atom by heating said ethane at temperature in the range of 500-610 C. while in the presence of CC14= in amount effective to promote dehydrochlorination and while in the absence of extraneously introduced elemental chlorine, and recovering an olefinic compound corresponding with said ethane.

4. The process for making an olefinic compound which comprises dehydrochlorinating a chlorofiuoroethane containing at least one hydrogen atom and at least one chlorine atom on adjacent carbon atoms by heating said ethane at temperature in the range of 500-610 C. while in the presence of C014 in amount in the range of 2-25% by weight based on the weight of said ethane and while in the absence of extraneously introduced elemental chlorine, and recovering an with said olefinic compound corresponding ethane.

5. The process for making an olefinic compound which comprises dehydrochlorinating a chlorofiuoroethane containing a CC1F2 group and at least one hydrogen atom on th adjacent carbon atom by heating said ethane at temperature in the range of 500-610 C. while in the presence of CC14 in amount in the range of 2-25% by weight based on the weight of said ethane and while in the absence of extraneously introduced elemental chlorine, and recovering an olefinic compound containing a CFz group.

6. The process for making CH2=CF2 which comprises dehydrochlorinating CHsCClFz by heating the same at temperature in the range of 500-6l0 C. while in the presence of CCh in amount in the range of 2-25% by weight based on the weight of said CHsCClFz and while in the absence of extraneously introduced elemental chlorine, and recovering CH2' '-CF2 from the re sultant reaction products.

7. The process for making an olefinic compound which comprises dehydrochlorinating a chlorofluoroethane containing at least one hydrogen atom and at least one chlorine atom on adjacent carbon atoms by heating said ethane at temperature in the range of 500610 C. while in the presence of C01; and metallic nickel both in amount effective to promote dehydrochlorination and while in the absence of extraneously introduced elemental chlorine, and recovering an olefinic compound corresponding with said ethane.

8. The process for making an olefinic compound which comprises dehydrochlorinating a chlorofiuoroethane containing a CClFz group and at least one hydrogen atom on adjacent carbon atoms by heating said ethane at temperature in the range of 500-610" C. while in the presence of C014 and metallic nickel both in amount 'efiective to promote dehydrochlorination and while in the absence of extraneously introduced elemental chlorine, and recovering an olefinic compound corresponding with said ethane.

9. The process for making an olefinic compound which comprises dehydrochlorinating a chlorofluoroethane containing at least one hydrogen atom and at least one chlorine atom on adjacent carbon atoms by heating said ethane at temperature in the range of 500-610 C. While in the presence of metallic nickel in amount effective to promote dehydrochlorination and in the presence of C014 in amount in the range of. 2-25% by weight based on the weight of said ethane, and while in the absence of extraneously introduced elemental chlorine, and recovering an olefinic compound corresponding with said ethane.

10. The process for making an olefinic compound which comprises introducing a chlorofluoroethane, containing at least one hydrogen atom and at least one chlorine atom on adjacent carbon atoms, into a reaction zone substantially packed with discrete bodies of metallic nickel,

dehydrochlorinating said ethane by passing the same through said zone, maintained at temperature in the range of BOO-610 0., while in adminture with C014 in amount eifective to promote dehydrochlorination and while in the absence of extraneously introduced elemental chlorine, discharging reaction products from said zone, and recovering from said products an olefinic compound corresponding with said ethane.

11.'Ihe process for making an olefinic compound which comprises introducing a chlorofiuoroethane, containing a CC1F2 group and at iii 7 least'one hydrogen atom on the adjacent carbon atom, into a reaction zone substantially packed with discrete bodies of metallic nickel, dehydrochlorinating said ethane by passing the same through said zone, maintained at temperature in the range of 500-610 C., while in admixture with C014 in amount efiective to promote 'deh'ydrochlorination and while in the absence of extraneously introduced elemental chlorine, discharging reaction products from said zone, and recovering from said products an olefinic compound containing a CFz group.

12. The process for making an olefinic compound which comprises introducing a chloroiiuoroethane, containing at least one hydrogen atom and at least one chlorine atom on adjacent carbon atoms, into a reaction zone substantially packed with discrete bodies of metallic nickel, dehydrochlorinating said ethane by passing the same through said zone, maintained at temperature in the range of 500-610 (3., while in admixture with C014 in amount in the range of 2-25% by weight based on the weight of said ethane and while in the absence of extraneously introduced elemental chlorine, discharging reaction products from said zone, and recovering from said products an olefinic compound corresponding with said ethane.

13. The process for making an olefinic compound which comprises introducing a chlorofluoroethane, containing a CClFz group and at least one hydrogen atom on the adjacent carbon atom, into a reaction zone substantially packed with discrete bodies of metallic nickel, dehydrochlorinatin said ethane by passing the same through said zone, maintained at temperature in the range of 500-4310 0., while in admixture with CC14 in amount in the range of 2-25% by weight based on the weight of said ethane and while in the absence of extraneously introduced elemental chlorine, discharging reaction products from said zone, and recovering from said products an olefinic compound containing a CF2 group. 7

CHARLES E. MILLER.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name a Date 2,461,523 Coffman et a1 Feb. 15, 1949 2,478,933 Bratton Aug. 16, 1949 2,551,573 Downing et a1 May 8, 19 1 2,566,807 Padburg et a1 Sept. 4-, 1951 

1. THE PROCESS FOR MAKING AN OLEFINIC COMPOUND WHICH COMPRISES DEHYDROCHLORINATING A CHLOROFLUOROETHANE CONTAINING AT LEAST ONE HYDROGEN ATOM AND AT LEAST ONE CHLORINE ATOM ON ADJACENT CARBON ATOMS BY HEATING SAID ETHANE AT TEMPERATURE IN THE RANGE OF 500-610* C. WHILE IN THE PRESENCE OF CC14 IN AMOUNT EFFECTIVE TO PROMOTE DEHYDROCHLORINATION AND WHILE IN THE ABSENCE OF EXTRANEOUSLY INTRODUCED ELEMENTAL CHLORINE, AND RECOVERING AN OLEFINIC COMPOUND CORRESPONDING WITH SAID ETHANE. 